Detergent composition containing n-tris (methylol) methyl amides



I amen...

phates as builders.

United States Patent DETERGENT COMPOSITION CONTAINING N-TRIS (METHYLOL)METHYL AMIDES Charles H. Schramm, Hillsdale, NJ., assignor to LeverBfrtglhers Company, New York, N.Y., a corporation 0 ame No Drawing.Application January 31, 1956 Serial No. 562,602

17 Claims. (Cl. 252-137) There are two general types of detergentcompositions available on the market: light duty and heavy dutydetergents. Heavyduty detergents have the ability to remove st-ubbornsoil and prevent soil redeposition in laundering. .:These are allpurposedetergents, usually are available in powdered form, and containpolyphos- However, these detergents by virtue of their,polyphosphatecontent and their strong detergency tend to irritatesensitive skin and therefore are less favored by the housewife fordishwashing and fine laundering. To compete with soap for thesepurposes, light duty detergents have been formulated. These lack thepolyphosphate builders but have a detergency which is adequate fordishwashingand light laundering, and are not as hard on the skin. 1

Many light duty detergents have been made available in liquid form, assolutions of synthetic detergents containing a high concentration of theactive detergent. Such detergents possess special properties, and arequite attractive to the housewife because there is no need to dissolvethe detergent. A washing solution is obtainable simply upon dilution ofan easily measured portion of the concentrated liquid with water.

An important feature of both heavy and light duty detergents is theirsudsing power. Most housewives still rely upon the. sudsing of thewashing solution to tell them when the .detergencyis sufiicient, andwhen it has been exhausted. .This is particularly so in dishwashing, andthe standardized dishwashing tests are based upon this principle; theend point of the usual dishwashing test is the time when the suds nolonger completely cover the surface of the washing solution. As is wellknown, most synthetic detergents are deficient in sudsing power, andthis difficulty is usually overcome by incorporating an ingredient whichenhances suds. It is essential that the added ingredient be soluble inthe washing solution to a sufficient extent to permit the preparation ofsolu- Many such agents are Also, the agent should tions of washingconcentrations. very sparsely soluble in water. be stable to bleach ifit is to be useful in heavyduty detergents.

In accordance with the invention, synthetic detergent compositions areprovided which contain an N-tris- (methylol) methyl amide and an organicnonsoap detergent, as the essential ingredients. The nonsoap detergentis referred to hereinafter as a syndet. When the detergent compositionsof the invention are primarily intended for light duty purposes, theseare the only essential components of the composition. If the light dutycomposition is to be in liquid form, a solvent for the syndet and theN-tris(methylol) methyl amide will of course be present in an amount tocompletely dissolve them. When the detergent composition is formu t theinvention:

2,927,081 Patented Mar. 1, 196.0

lce

lated for heavy duty, detergent polyphosphates and supplemental buildersalso will be present.

The N-tris(rnethylol) methyl amides of the invention have the formula:

' onion where R is an aliphatic hydrocarbon radical, which can besaturated or unsaturated, and can have a straight or branched chain, andwhich has from nine to .fifteen carin which the acid is given asillustrative:

CHiOH CHaOH I n GHzOH CHrOH The following illustrates the procedure: 200grams oflauric acid was heated with 121 grams oftris-(hydroxymethyl)methyl amine, bot-hjof which are availablecommercially, at to 200 C. for 5 hours. The resulting product was thenrefluxed with a large excess of water to give a quantitative yield of N-tris-(hydroxymethyl)-methyl lauramide. Recrystallization fro-mchloroform yielded a pure product melting .at l15.21l5.8 C.

The following N-tris(rnethylol) methyl amides are typical, and can beused in the detergent compositions of onion ctnao onn-o-ornon CHzOHCHzOH CnHzaC ONH-C-CHzOH HgOH GHrOH 01.11.10 ONH-Q-C'HaOHI onion TheN-tris(methylol) methyl amide can be combined with any syndet to give adetergent composition- 3 well known in the art under this name. Theyhave the general structure where R is a straight or branched chainhydrocarbon radical having from 1 to about 24 carbon atoms, at least oneR having 8 to 24 carbon atoms, x is a number from 1 to 5, and may be anaverage number, and M is hydrogen, an alkali metal such as sodium,potassium and ammonium, such as ethanolamine, diethanolamine,triethanolamine, and hexylamine (a more extensive list is given infra).R can for example be methyl, ethyl, hexyl, isohexyl, octyl, tert-octyl,isooctyl, nonyl, decyl, dodecyl, or octadecyl.

One example thereof are the sulfonated polypropylene benzene alkanes,having an alkyl radical characterized by thebranched chain structure ofpolypropylene and attached by a tertiary alkyl carbon to the benzenering, and having the following general structure:

IMCHCHgR:

where M is hydrogen, an alkali metal or an organic amine cation, and Rand R are alkyl, of the type formula C,,H and at least one R is astraight or branched chain'polypropylene group, the whole alkyl groupcon- 7 are the Nacconols.

.The alkyl sulfates are characterized by the structure RSO M, where M ishydrogen or an alkali metal, i.e., ammonium, sodium, or potassium, or anorganic amine cation, and R is a straight or branched chain saturated orunsaturated hydrocarbon radical, suchas myristyl, palmityl, oleyl,stearyl, and lauryl, as well as the mixed alkyl radicals derived fromfatty oils, such as coconut oil fatty alkyl, tallow fatty alkyl,cottonseed oil fatty alkyl and fish oil fatty alkyl radicals. R usuallyhas from eight to eighteen carbon atoms, preferably from twelve tosixteen carbon atoms.

Another class of anionic syndets are the sulfated oxyethylated alkylphenols, which have the following general formula:

where R is a straight or branched chain saturated or unsaturatedhydrocarbon group having at least eight carbon atoms up to approximatelyeighteen carbon atoms, A is oxygen, sulfur, a carbonamide orthiocarbonamide group or a carboxylic or thiocarboxylic ester group, xis a number from three to eight, and M is hydrogen or an alkali metal,e.g., sodium, potassium, and ammonium, or an organic amine cation. Rcan, for example, be a straight or branched chain octyl, nonyl, decyl,dodecyl, tetradecyI or octadecyl group. When the ammonium or organicamine salts are used, somewhat higher concentrations of detergent canusually be incorporated in aqueous solution.

In addition to these there may be mentioned sulfonated castor oil,.esters and ethers of isethionic acid, 1,2-dihy- Where M is hydrogen oran alkali metal, i.e., ammonium, sodium, or potassium, or an organicamine cation, n is a small Whole number from one to about five,preferably two or three, R is hydrogen, or an alkyl, aryl, orcycloaliphatic group, such as methyl, and R is an alkyl or alkyleneradical, such as myristyl, palmityl, olelyl and stearyl. Sod1um palmitictauride, sodium palmitic methyl tauride, sodium myristic methyl tauride,sodium palmiticstearic methyl tauride and sodium palmitic methylamidopropane sulfonate have been found to be particularly suitable foruse in the comopsitions of the invention.

The anionic syndets can be used in the form of the free acid, which canbe neutralized in situ in the liquid detergent solution by addition ofan organic amine or ammonium hydroxide. They are also readily availableas the alkali metal salts, such as sodium, potassium and ammonium, andthese would generally be used. However, the ammonium or organic aminesalts may be more soluble, and in this event would be preferred,particularly from the standpoint of increasing the detergentconcentration to a maximum. The amine can be any of those listedhereinafter.

There may also be used, either alone or in admixture with the anionics,nonionic syndets such as polyoxyalkylene ethers, which retain theterminal OH groups, as the glycols, and in which the terminal OH groupsare substituted, as the mono and diethers thereof, such as thepolyoxyalkylene alkyl phenols, polyoxyalkylene fatty acid amides, andalkyl polyoxyalkylene oxyand thioether and oxyand thioester nonionicdetergents.

Many polyoxyalkylene glycol ether syndets have the following generalformula:

Where R is a straight or branched chain saturated or unsaturatedhydrocarbon group having from eight to eighteen carbon atoms or anaralkyl' group having a straight or sulfur, carboxylic ester andthiocarboxylic ester groups, R and R are hydrogen or methyl, and x is ,anumberfrom eight to twenty. R can for example be a straight or branched.chain octyl, nonyl, decyl, octadecyl, dodecyl,

tetradecyl, or hexadecyl group, or an alkyl aryl group such asoctylbenzene, nonylbenzene, decylbenzene, octadecylbenzene, etc.

When R is .alkyl it will be evident that the syndet can be regarded asder ved from an alcohol, mercaptan, oxy or thio fatty acid ofhighmolecular weight, by condensation with ethylene oxide, 2,3-butyleneoxide or 1,2-propylene oxide. Typical of this type of alkyl ether arethe condensation products of oleyl or dodecyl alcohol or mercaptan withfrom eight to seventeen moles of ethylene oxide, such as Emulfor ON,Nonic 218 and Sterox SE and SK. Typical alkyl esters are G1226 and Renex(polyoxyethylene ester of tall oil acids), Sterox CD, Neutronyx 330 and331 (higher fatty acid esters of polyethylene glycol). I

When R is aralkyl, the syndets can be derived from an alkyl phenol orthiophenol.

The polyoxyalltylene alkyl phenols and thiopheno'ls havethe followinggeneral formula:

a tona'onwononn'cn-won oxide, available commercially under the tradenames NIW, Antarox A-400, lgepal CA and C0, Triton X-100, Neutronyx 600and Tergitol NPX.

Another class of nonionic syndets are Pluronics, which have thestructure:

These are fully described in U.S. Patent No. 2,674,619

to L. G. Lundsted, dated April 6, 1954; see especially column 3, lines55 to 71. See also U.S. Patent No. 2,677,700 to D. R. Jackson etaL,dated May 4, 1954.

m and m represent the average number "of oxyethylene units, and n theaverage number of oxypropylene units. See U.S. Patent No. 2,674,619. Thesum of m and m preferably is within the range from to 41, and npreferably is within the range from 17 to 3'1.

For light duty purposes, the detergent composition need not containdetergent polyphosphates or supple mental builders. Because ofsolubilityproblems, they will usually not be incorporated in liquiddetergent solutions. However, these can be added if desired to thepowders for heavy duty or other special purposes such as for use incertain waters. In the presence of polyphosphates, the N-tris(methylol)methyl amides improve the detergency of the 'syndct as well'a's'thesudsing.

Detergent polyphosphates are well known. The alkali metal, e.g., sodium,potassium and ammonium, salts are water-soluble. Sodium, potassium, andammoniumpyrophosphates, tripolyphosphates and t'etraphosphat'es areexemplary.

Typical supplemental builders are the alkali metal and alkaline earthmetal sulfates, chlorides, silicates, borates, carbonates,metaphosphates, and orthophosphates, such as sodium silicate, magnesiumsulfate, sodium tetraborate, sodium carbonate, sodium sulfate, trisodiumphosphate, potassium carbonate, disodium orthophosphate, sodiummetaphosphate, calcium sulfate, calcium chloride, sodium chloride,sodium borate and potassium metaphosphate. i

In addition to or instead of the above-mentioned supplement-al inorganicsalts, organic materials such as starch, polyethylene glycols, polyvinylalcohols, ethylhydroxyethyl cellulose, and salts ofcarboxymethylcellulose andcellulose sulfuric acid esters can be used assupplemental builders. It has been found that between about 0.1 and 1%of such materials is useful.

The ibuider mixture is so chosen that the. composition obtained in anaqueous 0.14% solution has a pH of 7 or above. Preferably, its pH lieswithin the range from 7 to about 10 since solutions which are morealkaline may be irritating to the skin and tend to weaken some fabrics,particularly woolens.

The powdered detergent composition is prepared by conventional methods,as by blending the ingredients thereof in an aqueous solution 'or slurryand then drying the resulting mixture in a spray or drum dryer atelevated temperatures. The N tris"(methylol) methyl amide may "be addedto the detergent composition at any stage of its manufacture, or to thefinished powder.

In the case of liquid detergents the ingredients may be dissolved inwarm water, or water-and-alcohol, or a1 cohol; they may be dissolvedseparately in alcohol or water, and then these solutions are mixed.Thereafter, the solution may be diluted to the desired concentration.The amount of solvent should be suflicient to dissolve all of the solidcomponents, and furnish a detergent solution which does not cloud orform a precipitate at temperatures as low as 45 F. The amount of totalsolids inthe composition is variable and is limited only by thesolubility of the components in the solvent. Usually, it is desirable tohave the syndet concentration as high as possible, and inasmuch as theN-tris (methylol) methyl amide improves the sudsing of the dependingupon-solubilityw Of this, the syndet should be within the range fromabout 23 to about 42% and the concentration of the N-tri(methylol)methyl amide should be within the range from about 8 to about 12%.--Wa'ter is the preferred solvent. When the solid syndet; andN-tris(methylol) methyl amide are "not sufliciently soluble in wateralone to produce the desiredlow cloud point their solubility may beimproved by the use of a mixture of water and a water-miscible lo'weraliphatic alcohol,'such as ethyl or methyl alcohol, watermiscibleglycols, such as ethylene glycol and diethylene glycol, as well as thea'lkylolamines. The latter solvents also make .it possible to controlthe pH, which usually should be within the range from about 7 to about10 for optimum detergency.

pH control also can be obtained by incorporating an inorganic base, suchas sodium, potassium or ammonium hydroxide, in the detergent, as well asorganic amines, such as methylamine, butylamine, hexylamine, and thelike. The amount of the base is not critical, but it is desirable-tohave sufficient base present to neutralize all free acids, includingdetergent acids and any free inorganic acid contaminants therewith, plusan excess amount to buffer acids encountered in washing and maintain areserve of alkalinity in the wash solution. In addition to this, ofcourse the amine may have solvent properties and be relied upon in partfor this function.

Exemplifying the amines useful for these purposes, as well as forpreparing salts of the anionic syndets supra, are water-soluble,strongly basic amines such as triethanol amine, diethanolamine,monoethanolarnine, ethylenediamine, .diethylenetriamine, tetraethanolammonium hydroxide, morpholine, mixed isopropanolamines, monoiso:propanolamine, diethylene glycol amine,'and amino ethyl ethanolamine.The alk-ylolamines, ether mono-, dior tri-, are preferred. 7'

"It may be noted that lower alcohols such as ethyl alco 1101 andpolyethylene 'glycols of low molecular weight may reduce the viscosityof the solution when used in small amounts. On the other hand,polyethylene glycols of higher molecular weight may tend to increaseviscosity even when employed in small amounts. Polyethylene glyco'lshaving a molecular weight within the range from to 60 00 are preferred,but as indicated the chain length is notcritical; those having lowermolecular weights aim bf used, for example, diethylene glycol andtriethylene g yco The composition may also contain dyestuffs andperfumes to suit the housewifes desire. It is customary to mask the odorof organic amines, and those skilled in the art are aware of perfumeswhich meet this need.

The following examples illustrate the invention.

In the examples the Dexter suds were determined using a Dexter twin-tubwashing machine, model 507 EPIDQ This is a vertical type agitator orwashing machine. The.

machine has a capacity of 16 gallons. Tests are con;

ducted on compositions containing 3 and 6 ounces of detergent per 16gallons of water. .The machine is filled with the 16 gallons of waterand the temperature adjusted to 120 F. The required amount ofconcentrated hard water stock solution is added to achieve the desiredhardness. Thereafter, the detergent is added, and 1 minute later 1 ounceof vacuum cleaner dust which has been dispersed in about 200 ml. ofwater by a motor driven stirrer is added and agitation continued for 1minute to insure thorough dispersion throughout the wash water.

Six pounds of clean dry cotton load cloth are added to the washer withthe agitator not running, to be sure that the load pieces are carefullydistributed throughout the machine and pushed below the surface of thewashing solution before the washing action is started. The machine isrun for 20 minutes during which time the suds are observed for volumeand'quantity. Readings are taken at 1 and 20 minutes. The highest ratingat any one time is 4, according to the following suds condition:

- No suds The total suds rating is the sum of all of these, or amaximumpossible total of 32.

The dishwashing test data were obtained using standardstainlesssteeldishpans. The dinner plates. are circular, 9 inches in diameter. Aboutto 5.5 grams of standard dishwashing soil are. spread evenly over thetop of each plate with a spatula. This soil is composed of 9. parts byweight of Covo, emulsifier-free, to which is added 8 parts by weight ofPillsburys bread flour and 1.25 ml. of green coloring for each pound offlour used, all thoroughly mixed.

4 The detergent composition is dissolved in 6 quarts of water of thedesired hardness and at the desired detergent concentration. The testsolution is brought to a temperature of 116 F. The plates are thenwashed by hand using freshly laundered dish cloths and washing iscontinued until the suds in the pan or solution no longer completelycover the surface of the water.

The Terg-O -Tometer detergency and sudsing were determined using theTerg-O-Tometer apparatus. The water bath temperature is adjusted to 124to 128 F., to bracket the standardized 125 F. washing temperature. Thepaddle oscillation is brought to 90 complete cycles per minute and thepaddle should oscillate through 320 of are.

With the agitators in position on the machine the detergent is added tothe washpot of the machine. From 1 to 4 grams of detergent to 1250 ml.of water usually is used. 1250 ml. of water of desired hardness is addedto the washpot containing the detergent after which the machine isstarted and the solution agitated until the detergent is dissolved.Eight pieces of soiled cloth approximately 4 /2" by 6" and four piecesof white unsoiled cloth of the same quality and size are added. Washingis continued for 20 minutes, after which the test swatches are removedfrom the solution and hand-squeezed. The washpot is refilled with clearrinse water of the same hardness used for washing at a temperature ofabout 130 F. and with the agitators running the cloths are rinsed for 1minute. The cloths then are removed, hand squeezed and ironed dry. Thereflectance of the soil cloths and of the white redeposition cloths ismeasured with a Hunter reflectometer using the green filter.

The results are calculated in this way: the average reflectance of theeight soiled test swatches'after Washing is taken. From this issubtracted the average of the soiled cloths before washing. Thedifference is the number of detergency units or DU. The reflectances ofthe four white redeposition pieces are averaged after washing, and thisaverage is the number of redeposition units or RU. The tests usually arerun at 3 ounce and 6 ounce concentration levels in and 180 p.p.m.hardness water.

The sudsing test in the Terg-O-Tometer is run in a way similar to thatin the Dexter washing machine. A 10 and 15 and a 20 minute reading istaken. Bleach is added at 15 minutes so that a decrease in the readingsbetween 15 and 20 minutes indicates susceptibility of the product tobleach. An approximation between the total Dexter and totalTerg-O-Tometer suds can be obtained with the following formula using thetotal 10 and 20 minute readings at both levels in both waters. Dextersuds equals 1.26XTerg-O-Tometer suds-l-4'.

EXAMPLES 1 TO 12 A group of twelve compositions were prepared byslurrying the following ingredients in the amounts indi- 'cated in waterand then drum drying.

Table I Percent by weight Control Examples Sodium -Oronite (sodiumphenyl polypropylene sulfonate, polypropylene alkyl having an average of12 to 15 carbon atoms) p 18 13 N-tris(methylol) methyl amide indicatedin 1 Table TI 2 to 5 Sodium toluene sulionate 2. 5 2. 5 Tetrasodiumpyrophosphate 30 30 Pentasodinm tripolyphosphatd, 15 16 R. U. Silicate(Na O'2 48102) 6 e Sodium carbonate 3 3 Sodium carboxymethylcellulos 0.5 0. 5 Sodium sulfate and miscellaneous.. 14. 5 14. 5

These were tested for suds by the standard Dexter test and fordishwashing by the standardized dishwashing testdescribed above, andcompared with the control composition containing no trimethylol methylamide.

The suds ratings wiven in the table below are the total of the Dextersuds readings at 3 and 6 ounce concentrations in both 50 and 180 p.p.m.hardness water. The numberof dishes washed is the total of the resultsat both 10 and 30 gram concentrations inboth 50 and 180 p.p.m. hardnessWater.

Table II N-tris(methylol) methyl amide CHsOH R-C ONH-(iJ-CHzOH CHzOHExample Percent Dexter Total N o. by R derived from- Total Dishes weightSuds Gontrol None 1O 96 1 3. 5 Tallow fatty acids..- 8 89 3. 5 Hardenedtallow fatty acids 5 89 3. 5 Steario acid 4% 68 3. 5 Oapric acid 13% 1363. 5 Coconut oil fatty acids 16% 141 3. 5 Coconut oil bottoms fattyacids (Palruitic-olelc mixture) 14% 3. 5 Laurie acid.-. 20 164 3. 5\dyristic acid. 21 148 2.0 18 148 3. 0 21% 163+ 3. 5 20% 161 4. 0 21%167+ 6.0 22% 170+ 1 Predominantly palmitic, small amount of oleio.

newest 9 The above :resul'ts :show that an enhanced sudsin'g isobtainedwith N-tristmethylol) methyl amides in which the R :radical hasfrom nine to fifteen carbon atoms. The laurie, myristi'c and mixedlauricmyristic composi- 10 The data show that the addition of 2%N-tris(methylol) methyl lauramide .gives a noticeable boost in bothsudsing and dishwashing. 4% of the amide gives a-substantial boost inthese properties. At the 4% level the tions .are the best. ThevN-tris(methylol.) methyl amide 5 N-tris'(methylol) methyl mixed laurican'd myristic derived from stearic acid is relatively poor, and so areamides is about equal to the N-tris(methylol) methyl those derived from.tallow, and .harden'e'dtallow, probably .lauramide both .in dishwashingand in sudsing. The 4% due to their eighteen carbon atom acid content.The N-tris(methylol) methyl palmitic-oleic amide is less satis- N-ti'is(metliylol) methyl amides derived fr'orn capric, factory indi'shwashing, although satisfactory in 'sudsing. coconut oil and coconutoil bottoms acids are inter- These .N-tris(methylol) .inethyl amides canbe used mediate. in conjunction with other suds boosters, such ascoconut The results for the mixed lauric and rn-yristic N-tris oil fattyacids glycine and coconut oil fatty acids a t (methylol) methyl amidesshow that 3 /2 parts of the amide. 'The former formulations are notsusceptible to N=tris('m'ethylol) methyl amide by weight of thecombleach as is the coconut oil fatty acid glycine alone. position issufficient, and that while more may be used Thecoconut-oil fatty acidaoetamide is deficient in dishno advantage is obtained using largeramounts. washing but .in combination with. an N-t-sistmethyf-lol.)

methyl amide this deficiency is overcome.

EXAMPLES 13 TO 16 EXAMPLES 17 AND 18 A group of compositions was made upby slurrying 0 Samples were prepared by slurrying the following inthenamed ingredients in water and drum drying: "g'redien't's in Wateranddrum "drying.

iTable JV Control Control coma Example; central ns'am'pie A B 0 17 D 18Pereentby weight I. Sodium bronite (sodium phenyl polypro pylenesulfonate, polypropylene alkyl hav- H ing an average of 12 17015 carbonatoms)....; 18 i i 18 B i 9 Sodium tallow sulfate -1 7 7 Ntris(methylol)methyl lauramide-xii'ytistamide. "as 1 Sodium toluene sulfonate 2. 5 2.5 2,5 I 1 Tetzasodiurn 'pyrupliosphate..- 30 J 1 .30. 30 30Pe'utasodiumt'ri olyphosphate. 15 a 15 1'5 15 15 R. U. Silieate(a,0;2.4sio,) s 6 s s a s is Sodium carbonate 3 3 3 31. y 3 3 Sodiumcarboxymethylcellulose 0. 5 -0. 5 0.5 0. 5 055- 0.5 Sodium sulfate andmiscellaneous.-. 14.5 14.5 14. 53 1435 11.5 14.15

These formulations were tested .for sudsi-ng and de- Ingredient Perceu ttergency by the standardized Terg-O-Tometer tests and i dishwashingtests described above.

Sodium om ts (sodium phenyl polypropylene sulfonate i s plolyprfipygene31th]? ha tvifig mp: 121trot15 carbo'n atoms) 2 Table .V 0 111m at one ao wa yac su ae N-trismisthylbn methyl amide (See Table III)- 0to4 -TMETERSUDS geutasogium tripolypholsp liate etraso 111111 pyrop osp 8.8...... R.U. silicate (NmOtSiOz 1:2.4) 6.0 v P-DJII- 0 ppm. Sodium carbh a; itiggrffiffi MW 7; 0 so. a m, Sodium sulfate and miscellaneousBalance 59 10' 15 20' 10' 15' 20' 10' 15' 201 10' 15' 20' Suds data wereobtained by the Dexter washing mal chine test and by the dishwa'sh-i-ngtest described above. -Gontrol.A-.- -0 0 0 0 0 0 0 0 o In the tablewhichfollows the suds tatingsare the totals -i .8 g 8 8 8 8 g g g g of theDexter washing machine suds ratings at the 3 and Gontrolieh 0 0 o :5 :4:/z 0 0 0 1A s 6 ounce levels in 50 and 180 p.p.m. hard water and 2 /2the dishwashing ratings are the total of the number of ""{i/ 1A 1% 1% }4y 1 1 1 dishes washed at the 10 and 30 gram levels in 50 and Controliil-2 g g g 180 p.p.m. hard water. A 25+ /2 9 0 1 60 0 AM-t 1 Table IIIN-tris(m'ethylol) methyl amide CHQOH TERG-O-TOMETER DETERGENCJYR-OONH-G-GH on 2 .50 p.p.m. 180 p.p.m. CHrOH I Composition 3 'oz. 6 oz.3 oz. 6 oz. Exlaqmple Percent Ra l a DBltte!" Dlsh- V i h weight ewe DURU DU RU DU RU DU RU N 28.9 79.3. 28.8 82.0 27.6 79.0 28.3 81.9 gonmlLaurie BGICL. 26.5v 79.7 25.5 80.4 23.8 79.5 25.0 -6 4 .-.-"do.l-t 27.180.3 25.3 78.8 26.9 '79.7 26.6 79.1; 4 W3 5???- 21 at a; 3% a; as as.22-; 4 c

9% sodium Oronite, 7% sodium tallow sulfate. 7 '7 11 12 DISHWASHING Theresults show that all of the amides tested have some boosting effect, asshown both in the dishwashing. and [Average of two runs] v Dexter sudsmgtests. However, none of the materials 50 180 mm are in any way aseffective as the N-tris(met hy1'ol) meth- Composition Total 5 yllauramide (Example 23) m accordance with the invention. g 30g. 10g 30 g.

I EXAMPLES 24 AND '25 COHtYOlA g g g 3 3 Three detergent compositionswere prepared by mixa 11 5 9 30 10 ing the ingredients named in thetable below in the f fig 8+ 2g amounts indicated in an aqueous slurryand drum drying. 34 17 32 9s Table VII The improvement obtained usingthe N tris(methylol) 15 methyl amide of the invention in Examples 17 and18 is evident. Control Example No,

I I EXAMPLES 19 to 23 I 24 25 A group of formulations were made upcontaining Sodium Q -o 1t d1um phenyipoly. ropylene s lfonate,polypropylene N t r1s(methylol) methyl amide and analogous alkanol g kylgua average of 12 to 15 amides for comparison purposes. These amideswere cgrhon atoms) u 9,0 9.0 9, So lurn tallo ftt cl su ate 8.0 8.0 8.0ncorporated individually indrum dried formulations hav fl z laummide 4 0mg the following cOmPOSlUOIl: 25 Nqnonoethanol lam-amide 4.0gentasolilum trlpolgpholspliate g g g e raso um pyron 051) a e sod; o t1 I perclem by lwelght g3 sl1icatte)(N?1O 24s10--- $8 3. 2.

mm rom e so 1um p eny po ypropy ene su o um car onae fonate p yp pyalkyl having an average of I iigigr f.fifl ii ffi flff i i-122: 313 313$23 12 to 15 carbon atoms) 18.0 Sodium sulfate and mls to 100.0 to 100.0to 100.0 Alkanol amide I I 3.5 Sodium toluene sulfonate 2,5 Mlsc.includes inert materials introduced with raw material. Tetrasodiumtripolyphosphate ,I15.0 v Tetrasodium pyrophosphate 30.0 Thecompositions were tested in accordance with the R.U. Silicate(NagO:2.4SiO 6.0] 'Dexter sudsing test with the following results:Sodium carbona 3.0 Sodium carboxymethylcellulose 0.5 T

l able VIII Sodium sulfate and misc. 14.5 H O 7.0

a I I I Example No. Misc. includes tree tatty acid introduced with theraw 40 control materials.

The alkanol amides used are listed in the table below. 1% 1, 2% 2 1% Theformulations were evaluated by the Dexter sudsing momma-50 "l 2 2611 2test and the dishwashing test described above.

Table VI Dexter Sudslng Test Dlshwashlng Test Example No; Alkanol Amidep.p.m; 180 p.p.m. 50 p.p.m. 180 p.p.m.

7 30:. 602. 302. 602. 10 gm. 30 gm. 10 gm. 30 gm.

Control No amide $6.16 2, 2 x, at 2,2 s 40 7 41 I CHIOH 1a c,,11,,-c1-r-rn---o--cm I 114,114 214,215 1%, 114 214.2% 11 60 18 so CHgOH 20C1lHu-CINHCHCHIOH 1,1 214,2: 54,1 295.2% 12 52 12 52 CHIOH 21 C11Hn--('IJNH-C-C;Hg 1%, 1% 2%, 2% 1%, 1% 2%, 2% 15 53 16 55 I CHzOH 22C11H;1C-NH-CHCH1OH 1%, 1% 2%, 2% 1%, 1% 2%, 2% 17 18 60+ GHaOH I 23CnHfl-(f-NH-C-CHgOH 2, 2% 3,11% 2,2 3,35 21 60+ 22 60+ CHzOH 1 Average01 2 W8.

13 The above :data shows that the N-tris(methylol) methyl lauramide ofthe invention is superior tothe lauric :monoethanol amide, The latterisno better than the control.

EXAMPLE 26 The ingredients mentioned below were mixed in a slurry anddrum dried.

1 Misc. includes free fatty acid material.

These formulations were tested in the Dexter sudsing and dishwashingtests described above with the following results:

The results show that the N-tris(methylol) methyl lauric and myristicamide is effective as a booster in com bination with the sulfateddetergent. There is no significantly increased sudsin and dishwashing.capacity at the high usage levels (6 ounce level in sudsing and 30 gm.level in dishwashing in both 50 ppm. and 180 ppm. hard water).

EXAMPLES 27 AND 28 These are examples of highly concentrated liquiddetergents.

Percent by weight Example No. Control Phenyl polypropylene sulfonicacids (alkyl of 12 to 15 carbon polypropylene, 100% active.) 26 5 25. 525. 5 Antaron K460 A (ammonium salt of sulfated oxyethylated nonylphenol, prepared from condensation of nonyl phenol with five moles ofethylene oxide, 57%

active) 15.0 15.0 15. N -tris (methylol) methyl lauramide-myristamide1:1 10.0 N-trisunet ylol) methyl capramide 10.0 Ethyl alcohol 15.0 15.015.0 Potassium hydroxide (86.4% alkali). 5. 0 5. 0 5.0 Water, perfume,ctc 39. 29. 5 29. 5

6 gms 33, 34

14 These compositions remain clear at .tcmperatures as low as 35 andhave a pH of 7.2 at 26 C. In place of potassium hydroxide, ammoniumhydroxide or triethanolamine could be used.

These formulations have excellent dishwashing capacity, as the followingdata show:

Plates washed in 120 ppm. at- Control Example No.

All parts and percentages in the specification and claims are by weight,and when with reference to components of the detergentcomposition arebased on the weight of the composition unless otherwise indicated.

I claim:

1. A nonsoap detergent composition consisting essentially of an amountof a synthetic organic nonsoap detergent selected from the groupconsisting of anionic nonsoap and nonionic nonsoap detergents to impartdetergency to the compisition and an amount from 0.5 to about 15% of thetotal composition and suflicient to enhance the sudsing of the syntheticdetergent of an N-tris(methylol) methyl amide having the formula:

where R is an aliphatic hydrocarbon radical having from nine to fifteencarbon atoms.

2. A nonsoap detergent composition in accordance with claim 1 in whichthe N-tris(methylol) methyl amide is N- tris(methylol) methyl lauramide.

3. A nonsoap detergent composition in accordance with claim 1 in whichthe N-tris(methylol) methyl amide is N-tris(methylol) methylmyristamide.

4. A nonsoap detergent composition in accordance with claim 1 inwhichthe N-tris(methylol) methyl amide is N-tris(methylol) methylcoconut oil fatty amide.

5. A nonsoap detergent composition in accordance with claim 1 in whichthe synthetic detergent is an anionic synthetic detergent.

6. A nonsoap detergent composition in accordance with claim 1 in whichthe synthetic detergent is a nonionic synthetic detergent.

7. A nonsoap detergent composition in accordance with claim 5 in whichthe anionic synthetic detergent is an alkyl aryl sulfonate.

8. A nonsoap detergent composition in accordance with claim 5 in whichthe anionic synthetic detergent is an alkyl sulfate.

9. A nonsoap detergent composition in accordance with claim 5 in whichthe anionic synthetic detergent is a detergent sulfated polyoxyalkylenealkyl phenol.

10. A nonsoap detergent composition in accordance with claim 6 in whichthe nonionic synthetic detergent is a detergent polyoxyalkylene ether.

11. A nonsoap detergent composition in accordance with claim 6 in whichthe nonionic synthetic detergent is a polyoxyalkylene ether glycol.

12. A nonsoap detergent composition in accordance with claim 6 in whichthe nonionic synthetic detergent is a polyoxyalkylene alkyl phenol.

13. A concentrated light duty nonsoap liquid detergent composition whichremains clear and uniform without separation of solid materials at lowtemperatures consisting essentially of a solvent, a synthetic organicnonsoap detergent selected from the group. consisting of anionic nonsoapand nonionic nonsoap detergents in an amount to impart detergency to thesolution and an amount from 0.5 to about 15% of the total composition 15and sufiicient to enhance the sudsing of the synthetic detergent of anN-tris(methylol) methyl amide having the formula:

. omoH R-CONHCCH2OH CHQOH where R is an aliphatic hydrocarbon radicalhaving from nineto fifteen carbon atoms.

14. A heavy duty nonsoap detergent composition con sisting essentiallyof an amount of a synthetic organic non- :soap detergent selected fromthe group consisting of anionic nonsoap and nonionic nonsoap detergentsto impart detergency to the composition, a detergent polyphosphate, andan amount from 0.5 to about 15% of the total composition and sufficientto enhance the detergency and slidsing of the synthetic detergent of anN-tris(methv ylol) methyl amide having the formula:

OHJOH RC ONH-C-CHzOH V HaOH References Cited in the file of this patentUNITED STATES PATENTS Weisberg Nov. 23, 1943 2,334,852 2,527,076 PrestonOct. 24, 1950 2,587,546 Matuszak Feb. 26, 1952 2,607,740 Vitale Aug. 19,1952 2,757,143 Katzman July 31, 1956 FOREIGN PATENTS 414,403 GreatBritain July 30. 1934 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 2,927 ,081 March 1, 1960 Charles H. Schramm It ishereby certified that error appears in the printed specification of theabove numbered patent requiring correction and that the said LettersPatent should read as corrected below.

Column 5 line 24,- in the formula, for "m'' second occurrence read mcolumn 8, line 45 for "when" read given column 10, line 56, Table V,vExample N0. 17, seventh column thereof, under the heading "5O p. p,m."and subheadings "6 02,-" and "20 "3 for "V read 1 same Example N0. 17,line 56, tenth column thereof under the heading "180 p. p.m.-" andsubheadings, 3 oz. and "20 5 for 1" read V column 13 line 30, Table X inthe heading, for "Deuter" read Dexter column 14 line 24 for compisition" read composition Signed and sealed this 30th day of August 1960.

(SEAL) Attest:

ERNEST W. SWIDER ROBERT C. WATSON Attesting Officer Commissioner ofPatents

14. A HEAVY DUTY NONSOAP DETERGENT COMPOSITION CONSISTING ESSENTIALLY OFAN AMOUNT OF A SYNTHETIC ORGANIC NONSOAP DETERGENT SELECTED FROM THEGROUP CONSISTING OF ANIONIC NONSOAP AND A NONIONIC NONSOAP DETERGENTS TOIMPART DETERGENCY TO THE COMPOSITION, A DETERGENT POLYPHOSPHATE, AND ANAMOUNT FROM 0.5 TO ABOUT 15% OF THE TOTAL COMPOSITION AND SUFFICIENT TOENHANCE THE DETERGENCY AND SUDSING OF THE SYNTHETIC DETERGENT OF ANN-TRIS(METHYLOL) METHYL AMIDE HAVING THE FORMULA: